Crystallization Of Thin Films Research Articles

Thin film sputter-deposition of AlN crystals in oxygenated chamber: A pilot study

Abstract Aluminium nitride (AIN) is a promising thin film electrical insulation material layer in electronic devices. The magnetron sputtering method is usually employed to sputter-deposit AlN thin film on silicon (Si) substrate using a pure aluminium (Al) metallic target in a low base pressure vacuum condition. In many cases, the thin film deposition of high quality AlN crystals requires the application of heat and bias to the substrate, highly pure nitrogen reactant gas, argon sputtering gas and Al target, low sputtering pressure, high sputtering power, post-deposition AlN annealing, ultra-low base pressure of the sputtering chamber and a distinctive crystal orientation of the nucleation layer or substrate underneath. In our work, the utilisation of AlN ceramic target instead of pure Al metallic target has allegedly facilitated the growth of AlN crystals without the need to conform to these requirements. Non-amorphous AlN〈100〉 and AlN〈002〉 thin film crystals have been successfully sputtered from AlN ceramic target on Si〈100〉 substrate in a relatively high sputtering chamber base pressure and at a moderate 200 W - 250 W of sputtering power. Additionally, 250 W of sputtering power has been observed to assist in the growth of AlN〈002〉 crystals. The presence of AlN〈002〉 may have reduced the leakage/tunnel current density in AlN thin film layer to 46.33 pA/cm2 and modified the small-scale surface height characteristics. A high degree of AlN〈002〉 crystallisation may suggest good electrical insulating properties in AlN thin film layer, which can be applied in electronic devices that critically require a low leakage current specification.

Piezoelectric MEMS microphones based on rib structures and single crystal PZT thin film

In this study, a controllable mass‒frequency tuning method is presented using the etching of rib structures on a single-crystal PZT membrane. The rib structures were optimized to reduce the membrane mass while maintaining the stiffness; therefore, the center frequency could be increased to improve the low-frequency bandwidth of microphones. Additionally, this methodology could reduce the modulus and improve the sensitivity for the same resonant frequency, which typically indicates the maximum acoustic overload point (AOP). The PZT film was chosen because of its greater density; the simulation results showed that PZT could provide a greater frequency tuning (24.9%) compared to that of the AlN film (5.8%), and its large dielectric constant enabled the optimal design to have small electrodes at the maximum stress location while mitigating the sacrificial capacitance effect on electrical gain. An analytical model of rib-structure microphones was established and greatly reduced the computing time. The experimental results of the impedance tests revealed that the center frequencies of the six microphones shifted from 74.6 kHz to 106.3 kHz with rib-structure inner radii ranging from 0 μm to 340 μm; this result was in good agreement with the those of the analytical analysis and finite element modeling. While the center frequency greatly varied, the measured sensitivities at 1 kHz only varied within a small range from 22.3 mV/Pa to 25.7 mV/Pa; thus, the membrane stiffness minimally changed. Moreover, a single-crystal PZT film with a (100) crystal orientation and 0.24-degree full width at half maximum (FWHM) was used to enable differential sensing and a low possibility of undesirable polarization. Paired with a two-stage differential charge amplifier, a differential sensing microphone was experimentally demonstrated to improve the sensitivity from 25.7 mV/Pa to 36.1 mV/Pa and reduce the noise from −68.2 dBV to −82.8 dBV.

Toward quantitative thermoelectric characterization of (nano)materials by in-situ transmission electron microscopy

We explore the possibility to perform an in-situ transmission electron microscopy (TEM) thermoelectric characterization of materials. A differential heating element on a custom in-situ TEM microchip allows to generate a temperature gradient across the studied materials, which are simultaneously measured electrically. A thermovoltage was induced in all studied devices, whose sign corresponds to the sign of the Seebeck coefficient of the tested materials. The results indicate that in-situ thermoelectric TEM studies can help to profoundly understand fundamental aspects of thermoelectricity, which is exemplary demonstrated by tracking the thermovoltage during in-situ crystallization of an amorphous Ge thin film. We propose an improved in-situ TEM microchip design, which should facilitate a full quantitative measurement of the induced temperature gradient, the electrical and thermal conductivities, as well as the Seebeck coefficient. The benefit of the in-situ approach is the possibility to directly correlate the thermoelectric properties with the structure and chemical composition of the entire studied device down to the atomic level, including grain boundaries, dopants or crystal defects, and to trace its dynamic evolution upon heating or during the application of electrical currents.

Design of an atomic layer deposition system with in situ reflection high energy electron diffraction.

We report the design, fabrication, and testing of an atomic layer deposition (ALD) system that is capable of reflection high energy electron diffraction (RHEED) in a single chamber. The details and specifications of the system are described and include capabilities of RHEED at varied accelerating voltages, sample rotation (azimuthal) control, sample height control, sample heating up to set temperatures of 1050 °C, and either single- or dual-differential pumping designs. Thermal and flow simulations were used to justify selected system dimensions as well as carrier gas/precursor mass flow rates. Temperature calibration was conducted to determine actual sample temperatures that are necessary for meaningful analysis of thermally induced transitions in ALD thin films. Several demonstrations of RHEED in the system are described. Calibration of the camera length was conducted using a gold thin film by analyzing RHEED images. Finally, RHEED conducted at a series of increasing temperatures was used to monitor the crystallization of an ALD HfO2 thin film. The crystallization temperature and the ring pattern were consistent with the monoclinic structure as determined by separate x-ray diffraction-based measurements.

The pulse Sn-assisted growth promotes the preparation of high-quality single-crystal ε-Ga2O3 films using MOCVD technology.

The single crystal ε-Ga2O3 thin films were successfully grown on c-plane sapphire substrates using metal-organic chemical vapor deposition (MOCVD). By employing the pulse method to introduce Sn as a growth adjuvant, the issue of phase mixing between β and ε phases, which commonly occurs when high-purity oxygen is used as the oxygen source in MOCVD, was effectively resolved. The physical phase composition, film surface quality and thickness of the epitaxial films of three sets of samples (not Sn, pulse Sn, direct Sn) were characterized using X-ray diffractometer, atomic force microscope and scanning electron microscope. High-quality ε-Ga2O3 single-crystal thin films were obtained under the conditions of Sn-assisted growth using the pulse method, resulting in a 51% increase in the epitaxial growth rate. Elemental analysis through X-ray photoelectron spectroscopy, combined with Gibbs free energy changes, that insight into the role of elemental Sn in the reaction. Through comparison and analysis, it was found that pulsed Sn is more fully involved in the reaction and plays a more efficient role than the direct Sn. The concentration of elemental Sn in the epitaxial film was analyzed using SIMS tests, from the substrate interface to the surface of the film, the Sn element exhibited a gradual accumulation toward the surface. The microstructures of the different samples were compared by transmission electron microscopy. Additionally, the reason that Sn elements promote the formation of ε-Ga2O3 single crystal was explained from the perspective of structure.

Preparation and Characterization of Nanostructured ITO Thin Films by Spray Pyrolysis Technique: Dependence on Annealing Temperature

Transparent conducting oxides (TCOs) like Indium tin oxide (ITO) have wide attention from all scientists which have low resistance and high visible light transmittance, used as transparent electrodes in many optoelectronic devices such as liquid crystal displays, touch screens, light emitting diodes, and solar cells. In this research, the relationship between the crystallization, optical transmittance, and surface roughness of nanostructured ITO thin films and the change in annealing temperature was investigated. To enhance the efficiency of this material in optoelectronic applications, both the optical transmittance in the visible region and the crystallite size must be increased. These results can be obtained by the heat treatment of the films. Nanostructured ITO thin layer films have been successfully prepared at a substrate temperature equal to (350)℃ by chemical spray pyrolysis (CSP) technique. The physical characterizations of nanostructured ITO thin layer films were investigated at different annealing temperatures (400,450 and 500)℃. The presence of diffraction peaks indicates that the as-deposited and post annealed films are polycrystalline cubic structure and the peak (400) is a preferred growth orientation. For all samples the value of intensity of diffraction peaks increases with increasing substrate temperature. The crystallite size of nanostructured ITO thin films is strongly related to the annealing temperature. The crystallite size estimated from XRD was found to rise with rising annealing temperature. The surface roughness of nanostructured ITO thin layer films increases with rising annealing temperature. High values of transmittance have been measured in the visible region 550 nm equal to (70, 82, 84 and 88)% corresponding to annealing temperature (350,400,450 and 500)℃ respectively.

Mechanochromic 3D Soft Photonic Crystals Enabled Anticounterfeiting and Encryption Information Storage

AbstractInspired by the color‐changing abilities of natural organisms, this research focuses on the design and fabrication of mechanochromic liquid crystal photonic crystal thin films with periodic self‐assembly structures. Benefiting from its unique 3D self‐assembled structure with a body‐centered cubic lattice, BP I film exhibits excellent mechanical properties, characterized by superior elasticity and toughness due to the presence of rigid and flexible microdomains and suitable dislocation line volumes. As the strain increases, the structural color of the BP I film demonstrates a repeatable and rapid shift from red to blue, covering the entire visible light spectrum with high reflectivity. The incorporation of fluorescent molecules further enhances the mechanical properties and endowing the film with circularly polarized luminescence under UV light irradiation. Utilizing different fluorescent dyes as inks, arbitrary patterned writing can be performed on the BPI film, enabling specific information hiding and encryption. The prepared label exhibits excellent environmental stability, presenting promising applications in information storage, anti‐counterfeiting, and flexible 3D displays. The study may contribute to a deeper understanding of the relationship between microstructure, mechanical deformation, and optical properties, potentially advancing the development of innovative responsive materials and multifunctional devices.

Constraining the Excessive Aggregation of Non-Fullerene Acceptor Molecules Enables Organic Solar Modules with the Efficiency >16.

Translating high-performance organic solar cell (OSC) materials from spin-coating to scalable processing is imperative for advancing organic photovoltaics. For bridging the gap between laboratory research and industrialization, it is essential to understand the structural formation dynamics within the photoactive layer during printing processes. In this study, two typical printing-compatible solvents in the doctor-blading process are employed to explore the intricate mechanisms governing the thin-film formation in the state-of-the-art photovoltaic system PM6:L8-BO. Our findings highlight the synergistic influence of both the donor polymer PM6 and the solvent with a high boiling point on the structural dynamics of L8-BO within the photoactive layer, significantly influencing its morphological properties. The optimized processing strategy effectively suppresses the excessive aggregation of L8-BO during the slow drying process in doctor-blading, enhancing thin-film crystallization with preferential molecular orientation. These improvements facilitate more efficient charge transport, suppress thin-film defects and charge recombination, and finally enhance the upscaling potential. Consequently, the optimized PM6:L8-BO OSCs demonstrate power conversion efficiencies of 18.42% in small-area devices (0.064 cm2) and 16.02% in modules (11.70 cm2), respectively. Overall, this research provides valuable insights into the interplay among thin-film formation kinetics, structure dynamics, and device performance in scalable processing.

Tailoring Crystallization Kinetics in Thin Sucrose Films during Convective Drying: Impact of Temperature and Humidity on Onset, Growth, and Nucleation Rate.

Drying experiments with varying air temperature and humidity were conducted to investigate the influence of the drying process on the crystallization of thin sucrose films. For the first time, the effects of the nucleation onset, nucleation rate, and growth rate were investigated in situ and their differentiated influence on product crystallinity could be assessed. The growth rate was not influenced by air humidity but showed a strong dependence on temperature. It increased with drying temperature; however, at high temperatures, growth was inhibited when the water content falls below a critical level. Noticeable differences in nucleation behavior could be observed with regard to air humidity. Dry air led to crystallization onsets at lower levels of supersaturation, while moderately humid air retarded it. At higher temperatures, nucleation onset commenced at lower water contents but at a constant supersaturation level. The nucleation rate doubled in experiments with moderately humid air (15% RH), while an elevated drying temperature showed generally lower nucleation rates. The observed differences in the nucleation onset and rate could be explained by the film-internal concentration profile, which is strongly influenced by drying parameters. The insights therefore provide a differentiated understanding of the formation of the physical state and how it can be influenced during convective drying.

Enhancing the Performance of Nanocrystalline SnO2 for Solar Cells through Photonic Curing Using Impedance Spectroscopy Analysis.

Wide-bandgap tin oxide (SnO2) thin-films are frequently used as an electron-transporting layers in perovskite solar cells due to their superior thermal and environmental stabilities. However, its crystallization by conventional thermal methods typically requires high temperatures and long periods of time. These post-processing conditions severely limit the choice of substrates and reduce the large-scale manufacturing capabilities. This work describes the intense-pulsed-light-induced crystallization of SnO2 thin-films using only 500 μs of exposure time. The thin-films' properties are investigated using both impedance spectroscopy and photoconductivity characteristic measurements. A Nyquist plot analysis establishes that the process parameters have a significant impact on the electronic and ionic behaviors of the SnO2 films. Most importantly, we demonstrate that light-induced crystallization yields improved topography and excellent electrical properties through enhanced charge transfer, improved interfacial morphology, and better ohmic contact compared to thermally annealed (TA) SnO2 films.

Enhancing Thermal Stability of Perovskite Solar Cells through Thermal Transition and Thin Film Crystallization Engineering of Polymeric Hole Transport Layers.

Organic hole transport layers (HTLs) have been known to be susceptible to thermal stress, leading to poor long-term stability in perovskite solar cells (PSCs). We synthesized three 2,5-dialkoxy-substituted, 1,4-bis(2-thienyl)phenylene (TPT)-based conjugated polymers (CPs) linked with thiophene-based (thiophene (T) and thienothiophene (TT)) comonomers and evaluated them as HTLs in n-i-p PSCs. TPT-T (MB/C6), which has branched 2-methylbutyl and linear hexyl (MB/C6) side chains, emerged as a promising HTL candidate, enabling power conversion efficiencies (PCEs) greater than 15%. In addition, PSCs with this HTL showed an improvement in long-term stability at elevated temperatures of 65 °C when compared to those with the state-of-art HTL, 2,2',7,7'-tetrakis(N,N-p-dimethoxyphenylamino)-9,9'-spirobifluorene (spiro-OMeTAD). This improvement is ascribed to the lack of thermal transitions within the operational temperature range of PSCs for TPT-T (MB/C6), which is attributed to the relatively short branched side chains of this polymer. We propose that the elimination of thermal transitions below 200 °C leads to HTLs without cracking as-deposited and after conducting a stress test at 65 °C, which can serve as a new design guideline for HTL development.

Au-induced crystallization of amorphous Ge thin films: An indication of the existence of a recrystallization process during growth at deep subeutectic temperature

The influence of Au catalyst microstructure on the crystallization behavior of Ge thin films obtained by Au-induced crystallization method is studied. By improving the Au catalyst crystallinity by pre-annealing, the hole mobility of Ge thin film crystallized at 200°C is improved to nearly 150 cm2/Vs thanks to the increase in Ge grain size, which is fairly high for a Ge film as thin as 10 nm. It is found that the increase in Ge grain size originates from the recrystallization process at deep subeutectic temperature. This is attributed to the existence of a metastable AuGe alloy phase surrounding crystalline Ge, which is kinetically stabilized by a continuous flow of Ge atoms through the alloy phase and realizes a solution-like growth. The process using a kinetically stabilized metastable phase will open up the possibility to realize a novel cost-effective and low-temperature process to fabricate high-performance semiconductor devices on plastic substrates.

Heat transport in SiCOH thin films: an experimental and molecular dynamics study

Carbon-doped silicon dioxide (SiCOH) film is currently regarded as one of the most promising low-k materials in the integrated circuits (ICs) industry for advanced technology nodes. However, there have been limited studies on the thermal properties of SiCOH compared to its electrical and mechanical properties. In this study, we investigate the thermal conductivity of SiCOH thin films through molecular dynamics simulations (MD) and experimental characterizations. Our findings indicate that the size effect on thermal conductivity at 300 K is negligible when the thickness of SiCOH film is less than 20 nm. Additionally, we observe a contrasting temperature dependence law for the thermal conductivity of SiCOH thin films compared to crystal SiO2 thin films. Furthermore, we demonstrate a significant decrease in thermal conductivity with increasing porosity in SiCOH films; specifically, an increase in porosity from 5.35% to 42.77% results in a 60% reduction in thermal conductivity. Moreover, we validate our simulation results by characterizing the thermal conductivity of SiCOH using 3 ω method.

Efficient High-Order Harmonic Generation from the van der Waals Layered Crystal Copper Indium Thiophosphate.

Layered metal thio- and selenophosphates (MTPs) are a family of van der Waals gapped materials that exhibit a multitude of functionalities in terms of magnetic, ferroelectric, and optical properties. Despite the recent progress in terms of understanding the material properties of these compounds, the potential of MTPs as a material class yet needs further scrutiny, especially in terms of nonlinear optical properties. Recent reports of efficient low-order harmonic generation and extremely high third-order nonlinear optical properties in MTPs suggest the potential application of these materials in integrated nanophotonics. In this article, we investigate the high-order nonlinear response of bulk and exfoliated thin-film crystals of copper indium thiophosphate (CIPS) to intense mid-infrared fields through experimental and computational studies of high-order harmonic generation (HHG). From a driving laser source with a 3.2 μm wavelength, we generate odd and even harmonics up to the 10th order, exceeding the bandgap of the material. We note conversion efficiencies as high as 10-7 measured for the fifth and seventh harmonics and observe that the harmonic intensities follow a power law scaling with the driving laser intensity, suggesting a perturbative nonlinear optical origin of the observed harmonics for both bulk and thin flakes. Furthermore, first-principles calculations suggest that the generation of the highest harmonic orders results from electron-electron interactions, suggesting a correlation-mediated enhancement of the high-order optical nonlinearity.

Recent Advances in Perovskite Single-Crystal Thin Film Optoelectronic Devices.

Among novel semiconductors, perovskites have gained significant attention due to their versatility, combining tunable optoelectronic properties with relatively easy fabrication processes. However, certain issues still hinder their widespread use, often related to the presence of defects and traps within the material. Beyond defect passivation in polycrystalline thin films, an alternative approach to enhancing material quality lies in the fabrication of single crystals. This review aims to provide an overview of the promising approaches explored to address specific challenges of perovskites that benefit from the single crystal nature, restricting our analysis to perovskite single crystal thin films (PSC-TF). We will discuss novel fabrication techniques and highlight recent achievements in devices, such as photodetectors, solar cells, and transistors. By examining the fundamental properties already discovered and showcasing the latest advancements, we aim to provide an overview of the perspectives and open challenges for PSC-TF in next-generation optoelectronic devices.

Tuning Van Der Waals Heterostructure of WS2/SrTiO3 Via in Situ Transmission Electron Microscopy

Monolayer two-dimensional (2D) materials have been widely researched and discussed in recent years, while multi-layers have received comparatively less attention. Nowadays, combining different materials to create heterostructures has become mainstream. In semiconductor industry, heterostructure can form devices such as lasers, light-emitting diodes, fast transistors and so on. Heterostructures can create well electronic properties by combining two different materials together. Therefore, heterostructures become a great tool to manipulate the electronic structures. In traditional heterostructures, the interfaces between two different materials are formed by covalent bonds, hence it requires similar lattice constants and structures. On the other hand, novel van der Waal heterostructures (vdW-heterostructure), formed by 2D materials, do not require the same strict similarity as traditional ones. VdW-heterostructures, which create 3D structures through van der Waals forces, provide a new perspective. In this study, we created a vdW-heterostructures by stacking tungsten disulfide (WS2) with single-crystal strontium titanate, SrTiO3 (STO), shown in Figure 1a,b. The crystalline atomic-layer WS2 and STO were synthesized by chemical vapor deposition (CVD) and pulsed laser deposition (PLD), respectively. They are analyzed by high-resolution transmission electron microscope (HRTEM) shown in Figure 1c-h. Once the vdW-heterostructures are formed, we conducted in situ heating by TEM. Through the advanced in situ technique, we observed the change of the twisted stacking angle by heating the vdW-heterostructure. Ultimately, the lattices will shift and rotate, minimizing the free energy, so that the vdW-heterostructure will be aligned and formed epitaxially. In addition, we utilized atomic resolution scanning transmission electron microscope (STEM) to identify the stacking images and the moiré pattern of the vdW-heterostructure. During the rotation, we can observed different moiré patterns by various twisted stacking angles. These different moiré patterns can produce different electrical properties, which can be applied to advanced semiconductor devices. Keywords: high-resolution TEM/STEM, in situ heating, 2D materials, van der Waal heterostructures, moiré pattern Figure 1. The vdW-heterostructure of STO/WS2. a) The diagram showing that the formation process of WS2/STO vdW-heterostructures which have different twisted stacking angles. b) The low-magnification SEM image showing that the single crystal STO thin film is transferred onto the TEM heating chips. The circles in the middle are the observation windows for transmission electrons. c-e) HRTEM images. f-g) Diffraction patterns of HRTEM. c,f) Single crystal STO thin film with d-spacing (1−10) = 0.284 nm. d,g) Monolayer single crystal WS2 with d-spacing (−110) = 0.274 nm. e,h) WS2(red)/STO(yellow) vdW-heterostructure with stacking angle 3.6°. Figure 1

(Invited) Modification of Dielectric Properties of Film Dielectric Materials by Solid Solution System

Compound semiconductor based power devices such as SiC and GaN require high temperature operating passive devices such as a capacitor. SiC-based active devices can operate above 250 °C. The development of high-temperature operational passives is urgently needed to advance to the module and system level. In the case of capacitors, currently available capacitors can only operate efficiently up to 175 °C. Therefore, a thin film capacitor that can operate at high temperatures and be monolithically integrated near the active device should be developed. In this talk, I will present our achievements in the development of high-temperature operating dielectric film materials using the solid solution system. One topic is A2B2O7 pyrochlore ferroelectrics. The ferroelectric materials with the pyrochlore structure such as Sr2Nb2O7 exhibited the high dielectric constant above 100 at high and low temperature ranges. However, due to the crystallographic direction dependence of the Curie-Weiss temperature, the temperature stability of the dielectric constant from room temperature to 300 °C was not available. In order to obtain the high temperature stability of dielectric constant from room temperature to 300 °C with high dielectric constant over 100, the pyrochlore ferroelectric solid solution thin films were investigated by employing the combinatorial synthesis. Composition spread thin films of solid solution of two or three kinds of materials were deposited on substrates by physical vapor deposition technique, which provided the systematic physical properties. High-throughput combinatorial synthesis method is effective in the rapid optimization of the correlation between the crystallization and the dielectric property change behavior. For the composition spread solid solution film, the Sr- or La-containing A2B2O7 pyrochlore ferroelectrics were selected from the viewpoints of ion radios and crystallographic direction dependence of the Curie-Weiss temperature. The composition spread films were formed on a Pt/Ti/SiO2/Si substrate by combinatorial RF sputtering with stoichiometric composition targets. The X-ray fluorescence spectrum of the composition-spread film showed a linear variation of the metal composition. After deposition, the samples were annealed at different temperatures under oxygen atmosphere to reduce oxygen vacancies and improve crystallinity. The crystallization of the composition-spread solid solution thin film was confirmed by X-ray diffraction patterns, indicating the composition dependence of the crystallographic orientation. Some compositions showed high dielectric constant over 100 and high temperature stability from room temperature to 300 °C. In the presentation, the correlation between film composition, orientation and dielectric constant will be discussed in detail. In the presentation, we also introduce our achievement of the BaTiO3 based relaxor ferroelectrics and other dielectric materials development using the solid solution system. For the relaxor ferroelectrics, among the BaTiO3 based relaxor ferroelectrics, we have selected x[BaTiO3]-(1-x)[Bi(Mg2/3Nb1/3)O3] . The permittivity of 400 and the stability <8% from room temperature to 400 °C were obtained, which are promising as high-temperature dielectric medium.

(Invited) Development of Single Crystal Nbn Superconductor on Wide Bandgap GaN By Sputtering and Thermal Annealing

The field of quantum computing is rapidly evolving, and Niobium Nitride (NbN) superconductors have emerged as a pivotal component in the field of quantum computing due to their unique properties. NbN possesses relatively higher superconducting transition temperature (Tc = 15-17 K) as compared to traditional superconductors, making it a promising material for various applications, including superconductor quantum computers, single photon detectors, and hot electron bolometers [1]. The investigation of NbN's superconductivity has been a subject of extensive research over the past few decades. Given that the properties of NbN are intricately linked to its crystal structure, lattice constant, and nitrogen content, precise control of the structural and electrical characteristics of NbN films is essential for the realization of NbN based quantum devices. The (111) planes of δ-NbN exhibit relatively small lattice mismatches with group-III nitride semiconductors (~0.2% for AlN and ~2.7% for GaN) [2], suggesting the potential for integrating crystalline NbN superconductors with nitride semiconductors on a single wafer. Notably, N-polar AlGaN/GaN high electron mobility transistors have been successfully fabricated on NbN films, operating under Tc with a negative differential resistance [3], indicating that the integration of nitride semiconductors and superconductors can be harnessed to create Josephson junctions. To achieve high-quality all-nitride NbN/group-III nitride/NbN Josephson junctions, a comprehensive understanding of the NbN/GaN heterointerfaces is crucial. Despite limited reports on the epitaxial growth of NbN films on nitride semiconductors, little is known about the structural and transport properties of such NbN films. Previously, MBE growth of NbN films have been demonstrated on GaN substrate, showing superconducting critical temperatures exceeding 10 K [4]. In this presentation, our efforts on the development of single crystal NbN thin films on wide bandgap GaN substrate using cost efficient sputtering technique followed by a subsequent high-temperature annealing will be presented. Commercially available single-crystalline GaN (0001)/sapphire templates as well as differently oriented (c and a-planes) sapphire substrates are used as the substrates for the sputtered deposition of NbN films at 20 °C. After the deposition, a high temperature annealing was performed separately at 950 °C for 30 mins under Ar as well as N2 atmosphere. While the as-deposited NbN film on GaN did not exhibit a discernible peak in the high-resolution XRD measurement, a high-intensity, single crystal (111)-oriented NbN film emerged prominently after annealing in both N2 and Ar environments. This suggests a notable enhancement in the crystalline quality of the superconducting material attributable to the thermal annealing process. Although the crystallinity of the NbN layer improves post-annealing, there is an associated increase in grain size and surface roughness. Preliminary findings indicate a reduction in the critical temperature of the NbN film from 12.82 K to 8.69 K after high-temperature annealing, potentially linked to the incorporation of impurities and crystallographic defects during this process. Further investigations using atomic resolution transmission electron microscopy, secondary ion mass spectrometry and X-ray photoelectron spectroscopy will be performed to investigate the influence of annealing duration, temperature, and conditions on the critical temperature, impurity incorporation and defect formation in NbN films deposited with different thickness.In continuation of our recent exploration into depositing crystalline superconducting NbN films on III-nitride semiconductors, this presentation will also focus on our recent advancement of ultrawide bandgap semiconductor materials such as the growth of high-quality quality β-Ga2O3 films and its ternary (AlxGa1-x)2O3 alloys, using metalorganic (MOCVD) and low-pressure (LPCVD) chemical vapor deposition growth techniques. Ga2O3 and (AlxGa1-x)2O3 have emerged as a promising semiconductor material platform for applications in high-power electronics and ultraviolet optoelectronics due to their excellent chemical and thermal stability, as well as high breakdown field strengths. The structural and electrical characteristics of Si-doped β-Ga2O3 and (AlxGa1-x)2O3 thin films will be presented. Additionally, we will present recent findings on achieving phase-pure β-(AlxGa1-x)2O3 films with a record-high Al composition (< 99%) [5]. Our research efforts into understanding the orientation-dependent Al incorporation in β-(AlxGa1-x)2O3 thin films and the determination of band offsets at β-(AlxGa1-x)2O3/β-Ga2O3 heterostructures will be presented. Furthermore, the presentation will touch upon the heteroepitaxial development of other phases of Ga2O3 and (AlxGa1-x)2O3, including α, γ, and κ. Acknowledgment: Dr. Bhuiyan acknowledges the support and guidance of his PhD advisor- Dr. Hongping Zhao at The Ohio State University for the MOCVD growth and characterization of β-Ga2O3 and (AlxGa1-x)2O3 films conducted in Zhao's group. Reference: Yamashita et al., Phys. Rev. Appl. 8, 054028 (2017).Kobayashi et al., Appl. Phys. Express 13, 061006 (2020).Yan et al., Nature 555, 183 (2018).G. Wright et al., APL Mater. 10, 051103 (2022).Bhuiyan et. al, Phys. Status Solidi RRL 17, 2300224 (2023). Figure 1

(Invited) Self-Discharge of Layered Oxide Cathodes Induced by Carbonate-Mediated Hydrogenation

Significant efforts have been made to improve the energy and power characteristics of cathodes in Li-ion batteries, while the research into cathode self-discharge has lagged behind. Self-discharge is the voltage drop experienced by all rechargeable batteries while stored in the charged state. The voltage drop becomes more problematic with increased cathode voltage and temperature. The physicochemical nature of internal reactions leading to cathode self-discharge is hardly understood and seldom discussed.To tackle this challenge, the structure and redox evolution of commercial LiNi0.5Mn0.3Co0.2O2 electrodes and single crystal cathode thin films upon the self-discharge in carbonate-based electrolyte is revealed by surface-sensitive X-ray scattering, spectrometric and electrochemical characterizations in conjunction with thermodynamic analysis. As evidenced by the interfacial toolkits and theoretical calculations, there is an evolution and growth of cathode surface reduction layer in different types of electrolyte after self-discharged from different potentials. Structural and chemical chacterizations as well as the elemental depth profiles within cathode thin film confirms proton-insertion-induced layered cathode hydrogenation. Calculation shows that such process is both thermodynamically and kinetically favorable and is triggered by the interfacial hydrogen atom abstraction of methylene group in carbonate solvent on delithiated cathode surface. A combination of experimental and theoretical studies reveals the carbonate-mediated cathode hydrogenation mechanism accounting for the voltage drop in the self-discharge. This offers additional understanding regarding defect generation and the degradation mechanism in layered cathodes beyond the traditional behaviors of lithium-diffusion-induced self-discharge and rock-salt phase induced cathode degradation. This study offers foundational knowledge of the interfacial degradation of cathode that can be translated to the rational design of improved cathodes and electrolytes, and the self-discharge mechanism studies in other electrochemical ion insertion materials and devices.

Influence of AZO buffer layer on characteristics of ZnO film on glass substrates for Schottky UV photodetector applications

An Al-doped ZnO (AZO) thin film was introduced into the structure of Ag/ZnO schottky Photo detectors (PDs) prepared by magnetron sputtering method on glass substrates. Influences of AZO layer on characteristics of ZnO film and performances of Ag/ZnO schottky PDs were discussed in detail. Results investigated by means of the scanning electron microscopy (SEM), X-ray diffraction (XRD) and Photoluminescence (PL) spectra show that the introduction of an AZO buffer layer can effectively decrease the defects and improve the crystallization of the ZnO thin film. Compared with Ag/ZnO schottky PDs, the Ag/ZnO/AZO PDs possess more excellent rectifying characteristics, the photocurrent (Iph) to dark current (Id) ratio are improved from 6.4 to 100.7. Given the bias voltage at -2 V, the photoresponsivity R and detectivity D* are increased from 0.15 A W-1 to 4.08 × 1010 Jones to 0.69AW-1 and 3.78 × 1011 Jones, respectively. The response speed becomes faster, the response and delay times are decreased from 281 to 395 ms to 178 and 300 ms, respectively. The results provide a new idea for the preparation of high performance ZnO film UV PDs on low-cost glass substrates.